Novel acaricide compositions

ABSTRACT

Novel acaricide compositions containing as the active ingredient, a synergistic mixture of (S)α-cyano-3-phenoxy-benzyl 1R, cis 2,2-dimethyl-3-(2&#39;,2&#39;-dibromovinyl)-cyclopropane-1-carboxylate and either 2,2,2-trichloro-1,1-di-(4-chlorophenyl)-ethanol or a mixed anhydride of benzoic acid and 3-chloro-2,6-dimethoxy-N-ethoxy-benzenecarboximidic acid and to a novel method of combatting acariens.

PRIOR APPLICATION

This application is a divisional of our copending commonly assigned U.S.patent application Ser. No. 35,811 filed May 4, 1979, now U.S. Pat. No.4,357,350, which in turn is a continuation-in-part of U.S. patentapplication Ser. No. 906,752 filed May 17, 1978, now abandoned.

OBJECTS OF THE INVENTION

It is an object of the invention to provide acaricide compositionshaving a synergistic activity.

It is a further object of the invention to provide an improved method ofcombatting acariens.

These and other objects and advantages of the invention will becomeobvious from the following detailed description.

THE INVENTION

The novel acaricidal compositions of the invention are comprised of anacaricidal amount of a synergistic mixture of(S)α-cyano-3-phenoxy-benzyl 1R, cis2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylate andeither 2,2,2-trichloro-1,1-di-(4-chlorophenyl)-ethanol or a mixedanhydride of benzoic acid and3-chloro-2,6-dimethoxy-N-ethoxybenzenecarboximidic acid and preferablyan inert carrier.

The said 3 components of the novel compositions are known compoundshaving acaricidal activity but it has been unexpectedly discovered thatthe claimed compositions have a clear synergistic activity againstacariens which are vegetable parasites such as Panonychus Ulmi whichattack vines and Tetranychus Urticae which attack beans. Tests haveshown that the acaricidal effects of the claimed compositions aregreater than the sum of the activity of the components individually.

The compositions of the invention have a great economical interest sincevery satisfactory acaricidal results are obtained with the compositionsof the invention at doses at which the individual components areineffective and therefore less of the active compound is required.

The compositions are generally effective against acarien parasites thatattack vegetables such as Panonychus Ulmi, Tetranychus Urticae,Tetranychus Cinnabarrinus, Tetranychus Atlanticus, Eotetranychus Carpiniand Bryobia Rubrioculus.

Among the preferred compositions of the invention are composition αcontaining 1 to 100 parts by weight of (S)α-cyano-3-phenoxy-benzyl 1R,cis 2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylate per100 parts by weight of 2,2,2-trichloro-1,1-di-(4-chlorophenyl)-ethanoland composition β containing 1.5 to 50 parts by weight of(S)α-cyano-3-phenoxy-benzyl 1R, cis2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylate per 100parts by weight of the mixed anhydride of benzoic acid and3-chloro-2,6-dimethoxy-N-ethoxy-benzenecarboximidic acid.

The compositions of the invention may be in the form of powders,granules, suspensions, emulsions and solutions containing besides theactive ingredients, other ingredients such as cationic, anionic ornonionic surface active agents, inert powders such as talc, clays,silicates or kieselguhr, a vehicle such as water, alcohol, hydrocarbonsor other organic solvents or animal, vegetable or mineral oil.

The novel method of the invention for combatting acariens comprisescontacting acariens with an acaricidally effect amount of composition αor composition β. The usual total effective dose for composition α is 10to 1000 g per hectare and for composition β is 150 to 350 g per hectare.

Among preferred compositions of the invention are the compositions α₁containing 1.25 to 25, most preferably 4.5 to 8.5, parts by weight of(S)α-cyano-3-phenoxy-benzyl 1R, cis2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylate per 100parts of 2,2,2-trichloro-1,1-di-(4-chlorophenyl)-ethanol and the saidcompositions are especially effective against the Panonychus species ata dose of 200 to 450 g per hectare. The said compositions may be appliedat a rate of 5 to 50 g of the said (S)α-cyano-3-phenoxybenzyl ester and200 to 400 g of the said substituted ethanol per hectare.

Another preferred composition of the invention which has been found tobe particularly useful against Tetranychus species are the compositionsα₂ containing 10 to 75, most preferably 25 to 50, parts by weight of(S)α-cyano-3-phenoxy-benzyl 1R, cis2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylate per 100parts by weight of 2,2,2-trichloro-1,1-di-(4-chlorophenyl)-ethanol andthe said compositions are applied at a total dose of 15 to 500 g perhectare. This corresponds to a dose of 5 to 25 g of the(S)α-cyano-3-phenoxy-benzyl ester and 100 to 300 g of the saidsubstituted ethanol per hectare.

A further preferred composition of the invention which has been found tobe particularly useful against Panonychus species are the compositionsβ₁ containing 4 to 16 parts by weight of (S)α-cyano-3-phenoxy-benzyl 1Rcis 2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylate per100 parts by weight of the mixed anhydride of benzoic acid and3-chloro-2,6-dimethoxy-N-ethoxy-benzenecarboximidic acid and the saidcompositions are applied at a total dose of 100 to 350 per hectare. Thisdosage corresponds to a dosage of 10 to 25 g of the said(S)α-cyano-3-phenoxy-benzyl ester and 100 to 200 g of the said mixedanhydride per hectare.

In the following examples, there are described several preferredembodiments to illustrate the invention. However, it should beunderstood that the invention is not intended to be limited to thespecific embodiments.

EXAMPLE 1

An acaricide composition was prepared containing 355 g/l of technical2,2,2-trichloro-1,1-di-(4-chlorophenyl)-ethanol, 12.75 g/l of technical(S)α-cyano-3-phenoxy-benzyl 1R, cis2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylate, 5 g/l of2,6-di-tert.-butyl-p-cresol, 80 g/l of Emcol AK 18-35 and 580 g/l ofxylene. Emcol AK 18-35 is a strong hydrophile emulsifier sold by thefirm Witco-chemical.

EXAMPLE 2

An acaricide composition was prepared containing 355 g/l of2,2,2-trichloro-1,1,-di-(4-chlorophenyl)-ethanol, 25.5 g/l of(S)α-cyano-3-phenoxy-benzyl 1R, cis2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylate, 10 g/lof 2,6-di-tert.-butyl-p-cresol, 80 g/l of Emcol AK 18-35, and 567.2 g/lof xylene.

EXAMPLE 3

An acaricide composition was prepared containing 216 g/l of technicalmixed anhydride of benzoic acid and3-chloro-2,6-dimethoxy-N-ethoxy-benzenecarboximidic acid, 12.75 g/l of(S)α-cyano-3-phenoxy-benzyl 1R, cis2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylate, 5 g/l of2,6-di-tert.-butyl-p-cresol, 35 g/l of Emcol H 300 B, 25 g/l of Emcol H500 B and 652.9 g/l of xylene. The 2 Emcol products are mixtures ofpolyoxyethylene ether and calcium alkylbenzenesulfonates.

EXAMPLE 4

An acaricide composition was prepared containing 216 g/l of technicalmixed anhydride of benzoic acid and3-chloro-2,6-dimethoxy-N-ethoxy-benzenecaboximidic acid, 25.5 g/l of(S)α-cyano-3-phenoxy-benzyl 1R, cis2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylate, 16 g/lof 2,6-di-tert.-butyl-p-cresol, 35 g/l of Emcol H 300 B and 25 g/l ofEmcol H 500 B.

EXAMPLE 5

The effectiveness of (S)α-cyano-3-phenoxy-benzyl 1R, cis2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylate (compoundA) and 2,2,2-trichloro-1,1-di-(4-chlorophenyl)-ethanol (compound B) andmixtures thereof was determined against Panonychus Ulmi using vines ofthe Sirah variety. The test was repeated 4 times for each dose using theblock method with an untreated control in each block. Each elementaryblock consisted of 10 vines and a single treatment was effected with abase of 1000 liters of spray mixture per hectare using a Van der Weijsprayer at a constant pressure. Reading were taken 7 days after thetreatment to determine the number of moving forms (larvae and adults)present on 15 leaves which were collected by brushing of the leaves andthe results were reported in a percentage of reduction of the populationas compared to the non-treated controls. The comparison usedemulsifiable concentrates containing 1.25, 2.5 and 5 g per hectoliter ofcompound A, emulsifiable concentrates containing 30 g/hl of compound Band mixtures prepared just before use of emulsifiable concentratescontaining 30 g/hl of compound B and 1.25, 2.5 or 5 g of compound B.

To show more clearly the synergistic effect, the Limpel formula was usedwhich permitted the evaluation of theoretical efficacity to be obtainedwith the combinations. Efficacity (E) of the association of P₁ +P₂ atdosages D₁ +D₂ is expressed with the percentage of efficacity (X)obtained with product P₁ at a dose D₁ and with the percentage ofefficacity (Y) obtained with product P₂ at dose D₂ or

    E=X+Y=XY/100

The experimental results and expected efficacity is reported in Table I.

                  TABLE I                                                         ______________________________________                                                           % Reduction of                                                                population of 7 days                                               Dose in    after Treatment                                            Compound  g/hl         Obtained Expected*                                     ______________________________________                                        A         1.25         38.6                                                             2.5          41.7                                                             5.0          50.0                                                   B         30           20.1                                                    A+       1.25+        80.5     51                                            B         30                                                                   A+       2.5+         65.4     53.4                                          B         30                                                                  Controls               492**                                                  ______________________________________                                         *Limpel method                                                                **Number living on 15 leaves                                             

The results of Table I clearly show the synergistic effect obtained bythe combination of compounds A and B.

EXAMPLE 6

The activity against Tetranychus Urticae was determined for compounds Aand B using bean plants having 2 bell leaves which were sprayed with 4ml of the test compounds equally on the 2 faces of each border. Beforethe spraying, a band of glue was placed at the joint of convergence oftwo petioles to prevent the escape of acariens. After the treatment, 25adult Tetranychus Urticae were placed on each leaf and 48 hours laterthe degree of mortality was determined. 9 days after the treatment, thedegree of ovicidal effect (% of eggs not opened) and the larvicidaleffect (% of mortality) was determined for the compounds. Two tests wereused for each dose and the results are reported in Table II as a percentof mortality and in Table II as a percent of reduction calculated asfollows: ##EQU1## wherein N₁ is the initial number of adults and N_(F)is the final number of living larvae and if N_(F) >N₁, the percentage is0.

                  TABLE II                                                        ______________________________________                                                 Compound A                                                           Compound B 0            0.625 g/hl                                                                              1.25 g/hl                                   ______________________________________                                        0          (1) 0.0      2.4       9.0                                                    (2) 1.4      0.7       37.8                                                   (3) 1.3      0.7       10.1                                        1.25 g/hl  59.8         73.4      80.0                                                   18.8         88.0      86.0                                                   8.7          8.7       16.7                                        2.50 g/hl  100          95.8      100                                                    37.5         93.0      88.3                                                   30.0         11.1      20.0                                        5.0 g/hl   100                                                                           62.2                                                                          58.1                                                               ______________________________________                                         (1) % of dead adults                                                          (2) % of closed eggs                                                          (3) % of dead larvae                                                     

                  TABLE III                                                       ______________________________________                                                 Compound A                                                           Compound B 0          0.625 g/hl                                                                              1.25 g/hl                                     ______________________________________                                        0          0          0         0                                             1.25 g/hl  0          73.4      94.7                                          2.50 g/hl  91.1       88.7      77.1                                          5.00 g/hl  83.3       --        --                                            ______________________________________                                    

The two Tables show the synergistic effect with Table III most clearlyshowing the synergism of compounds A and B. For example, at a dose of0.625 g/hl, compound A does not have any effect on the reduction of thepopulation and neither does compound B at a dose of 1.25 g/hl. However,at combined dosage of 0.625 g/hl of compound A and 1.25 g/hl of compoundB, a 73.4% reduction of the population is obtained.

To show the synergism in another manner, the Limpel formula was used todetermine the theoretically expected efficacity of the association andthe results are compared with the returned results in Table IV.

                  TABLE IV                                                        ______________________________________                                               Compound A                                                             Compound B                                                                             0       0.625 g/hl    1.25 g/hl                                      ______________________________________                                        0        0.0     2.4            9.0                                                    1.4     0.7           37.8                                                    1.3     0.7           10.1                                                            Actual  Expected                                                                              Actual                                                                              Expected                               1.25 g/hl                                                                              59.8    73.4    60.8    80.0  63.4                                            18.8    88.0    19.4    86.0  49.5                                            8.7     8.7     9.3     16.7  17.9                                   2.5 g/hl 100     95.8    100     100   100                                             37.5    93.0    37.9    88.3  61.1                                            30.0    11.1    30.5    20.0  37.1                                   ______________________________________                                    

The results of this test show the net synergistic effect with compoundsA and B. The larvicide effect is weak but they have an elevatedpercentage of mortality with adults and eggs and the final reduction ofpopulation is very high.

EXAMPLE 7

The acaricide activity against Panonychus Ulmi was determined forcompound A and the mixed anhydride of benzoic acid and3-chloro-2,6-dimethoxy-N-ethoxy-benzenecarboximidic acid (compound C)was determined as in Example 5 and the results are reported in Table V.

                  TABLE V                                                         ______________________________________                                                            % Reduction of                                                                Population 7 days                                                 Doses in    after treatment                                           Compound  g/hl          obtained expected*                                    ______________________________________                                        A         1.25          38.6     --                                                     2.50          41.7     --                                                     5.00          50.0     --                                           C         20.0          39.9                                                  A + C     1.25 + 20     71.5     63.1                                                   2.50 + 20     70.7     65                                           Control**               492                                                   ______________________________________                                         *Limpel formula                                                               **Number of living forms on 15 leaves                                    

The results of Table V clearly show the net synergistic effect of thecombination of compounds A and C.

Various modifications of the compositions and method of the inventionmay be made without departing from the spirit or scope thereof, and itis to be understood that the invention is intended to be limited only asdefined in the appended claims.

We claim:
 1. An acaricidal composition comprised of an acaricidallyeffective amount of a synergistic mixture of 1.5 to 50 parts by weightof (S)α-cyano-3-phenoxy-benzyl 1R, cis2,2-dimethyl-3-(2,2'-dibromovinyl)-cyclopropane-1-carboxylate and 100parts by weight of a mixed anhydride of benzoic acid and3-chloro-2,6-dimethoxy-N-ethoxy-benzenecarboxyimidic acid and an inertcarrier.
 2. A composition of claim 1 wherein the amount of the said(S)α-cyano-3-phenoxy-benzyl ester is 4 to 16 parts by weight.
 3. Amethod of combatting acariens comprising contacting the acariens with anacaricidally effective amount of a composition comprised of asynergistic mixture of 1.5 to 50 parts by weight of(S)α-cyano-3-phenoxy-benzyl 1R, cis2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylate and 100parts by weight of a mixed anhydride of benzoic acid and3-chloro-2,6-dimethoxy-N-ethoxy-benzene-carboximidic acid.
 4. The methodof claim 3 wherein a composition of claim 10 is applied at a rate of 100to 350 g per hectare.